Concerning the Lewis acidity of NO+ and NO2/+ as measured by their affinity to selected bases

Recently published theoretical results concerning the NO+ and NO2/+ gas-phase affinities of a few selected molecules, as well as the correlation between the above quantities and the corresponding proton affinities, are examined in the context of the much larger body of experimental and theoretical data already reported in the literature.Fil: Cacace, Fulvio. Università degli studi di Roma "La Sapienza"; ItaliaFil: Ciuffo, Gladys Maria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis. Universidad Nacional de San Luis. Facultad de Ciencias Físico Matemáticas y Naturales. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis; ArgentinaFil: De Petris, Giulia. Università degli studi di Roma "La Sapienza"; Itali

The Peroxymonocarbonate anion HCO4- as an effective oxidant in the gas phase: A mass spectrometric and theoretical study on the reaction with SO2

The peroxymonocarbonate anion, HCO4-, the covalent adduct between the carbon dioxideand hydrogen peroxide anion, effectively reacts with SO2 in the gas phase following three oxidative routes. Mass spectrometric and electronic structure calculations show that sulphur dioxide is oxidised through a common intermediate to the hydrogen sulphate anion, sulphur trioxide, and sulphur trioxide anion as primary products through formal HO2-, oxygen atom, and oxygen ion transfers. The hydrogen sulphite anion is also formed as a secondary product from the oxygen atom transfer path. The uncommon nucleophilic behaviour of HCO4- is disclosed by the Lewis acidic properties of SO2, an amphiphilic molecule that forms intermediates with characteristic and diagnostic geometries with peroxymonocarbonate

Isotope Exchange in Disulfur Monoxide-Water Charged Complexes: A Mass Spectrometric and Computational Study

A hitherto unknown, isotope-exchange reaction is studied in ionized gaseous mixtures containing disulfur monoxide and water. The kinetics, mechanism, and intermediate of the reaction are investigated by experimental and theoretical methods. The reactivity of the S2O˙+ cation with water is investigated under a wide range of pressures ranging from 10−7 to 10−4 Torr, by FT-ICR, TQ, and high-resolution CAD mass spectrometry. In the high-pressure limit the reaction proves to be a route to strongly bound sulfur-containing species

A study of the hydrostatic mass bias dependence and evolution within The Three Hundred clusters

We use a set of about 300 simulated clusters from The Three Hundred Project to calculate their hydrostatic masses and evaluate the associated bias by comparing them with the true cluster mass. Over a redshift range from 0.07 to 1.3, we study the dependence of the hydrostatic bias on redshift, concentration, mass growth, dynamical state, mass, and halo shapes. We find almost no correlation between the bias and any of these parameters. However, there is a clear evidence that the scatter of the mass-bias distribution is larger for low-concentrated objects, high mass growth, and more generically for disturbed systems. Moreover, we carefully study the evolution of the bias of twelve clusters throughout a major-merger event. We find that the hydrostatic-mass bias follows a particular evolution track along the merger process: to an initial significant increase of the bias recorded at the begin of merger, a constant plateaus follows until the end of merge, when there is a dramatic decrease in the bias before the cluster finally become relaxed again. This large variation of the bias is in agreement with the large scatter of the hydrostatic bias for dynamical disturbed clusters. These objects should be avoided in cosmological studies because their exact relaxation phase is difficult to predict, hence their mass bias cannot be trivially accounted for.Comment: 11 pages, 8 figures. Accepted for publication in MNRA

Author Correction: Allele specific repair of splicing mutations in cystic fibrosis through AsCas12a genome editing

An amendment to this paper has been published and can be accessed via a link at the top of the paper

CHEX-MATE:Morphological analysis of the sample

In this work, we performed an analysis of the X-ray morphology of the 118 CHEX-MATE (Cluster HEritage project with XMM-Newton - Mass Assembly and Thermodynamics at the Endpoint of structure formation) galaxy clusters, with the aim to provide a classification of their dynamical state. To investigate the link between the X-ray appearance and the dynamical state, we considered four morphological parameters: the surface brightness concentration, the centroid shift, and the second- and third-order power ratios. These indicators result to be: strongly correlated with each other, powerful in identifying the disturbed and relaxed population, characterised by a unimodal distribution and not strongly influenced by systematic uncertainties. In order to obtain a continuous classification of the CHEX-MATE objects, we combined these four parameters in a single quantity, M, which represents the grade of relaxation of a system. On the basis of the M value, we identified the most extreme systems of the sample, finding 15 very relaxed and 27 very disturbed galaxy clusters. From a comparison with previous analysis on X-ray selected samples, we confirmed that the Sunyaev-Zeldovich (SZ) clusters tend to be more disturbed. Finally, by applying our analysis on a simulated sample, we found a general agreement between the observed and simulated results, with the only exception of the concentration. This latter behaviour, is partially related to the presence of particles with high smoothed-particle hydrodynamics density in the central regions of the simulated clusters due to the action of the idealised isotropic thermal Active Galactic Nuclei (AGN) feedback

Atmospherically relevant ion chemistry of ozone and its cation

The importance of ionic processes that occur in terrestrial, planetary, and stellar atmospheres is receiving increasing recognition. Actually, ions play important, often crucial, roles in a variety of atmospheric processes throughout the universe, and a strong link with the neutral chemistry is also apparent. In the terrestrial atmosphere, the ionic reactions are most relevant in those transient and fleeting events, e.g., lightning, coronas (in thunderstorm clouds and along power lines), where the local ion density is much higher than in unperturbed air, and the chemical systems are typically far from equilibrium. In such cases, ozone, a key molecule for the terrestrial atmosphere, is also present in high local concentrations; it is formed from O2 by the same transient event. Accordingly, this review provides a survey of the positive ion chemistry of ozone with several of the most important ‘‘atmospheric’’ species: the reactions, the products, andthe importance of the examined processes are discussed also in the light of the local thermodynamic disequilibrium (LTD) approach to the chemistry of transient atmospheric events. In all such studies, mass spectrometry is traditionally, and remains today, theexperimental techniqueofchoice.Thenovel application of mass spectrometry to the study of neutral species (NRMS), highly successful for the preparation and positive detection of long-sought, otherwise inaccessible, short-lived neutrals, makes mass spectrometry the most powerful tool now available for the study of the species and processes that are relevant to atmospheric chemistry. Selected examples of the interlink between the neutral and the ionic chemistry are also illustrated

Mass spectrometric contributions to problems related to the chemistry of atmospheres

Recent mass spectrometric studies of species and processes relevant to the chemistry of atmospheres are reported. New species have been detected, including HO3; a stratospheric reservoir of OH radicals; the [H2O+O2-] charge transfer complex, central to the atmospheric photonucleation theory; and the OSOSO oxide and its cation, likely present in the Io's atmosphere, As to ionic processes, a new route to tropospheric N2O in air ionized by lightning and coronas is reported, as well as the complex chemistry promoted by ionization of ozone/freon and ozone/carbonyl sulfide mixtures and the formation of O-5(+), relevant to the problem of O-18 excess in stratospheric ozone